EP2899008A1 - Injection moulding method for the manufacture of a composite product with a structured surface in the contact area of the layers in order to improve adhesion - Google Patents

Abstract

The invention relates to a method for producing a composite component, comprising a carrier of a thermoplastic composition and a second layer, which is in direct contact with the carrier, wherein the surface of the carrier adjoining the second layer is structured. By structuring the adjacent surface, a surprising adhesion improvement is achieved. The method comprises the following steps: (i) injecting the melt of the thermoplastic composition into a first mold cavity for the production of the thermoplastic carrier, (ii) cooling the melt, (iii) enlarging the cavity of the injection molding tool to create a gap or converting the injection molding into a second cavity. (iv) injecting a mixture of raw materials to form the second layer in said gap space between the thermoplastic carrier and the tool surface, wherein the raw material mixture polymerizes to form the second layer in direct contact with the surface of the thermoplastic carrier, (v) demolding the composite part from the tool cavity, wherein the tool into which the thermoplastic composition is injected has, on its inner surface, a structure deviating from a smooth surface, by which the surface of the thermoplastic carrier obtains a structure.

Description

The present invention is a process for producing composite components comprising a thermoplastic composition carrier and a second layer having improved interlayer adhesion.

Thermoplastic carriers are provided in particular to improve the surface properties, haptics, optics, noise and heat insulation with another layer.

A known from the prior art method for producing composite parts with a thermoplastic support and a coating provides the coating immediately after the preparation of the carrier by injection molding in the same machine before. After the carrier has been injection-molded, the cavity around the carrier is enlarged and the composition for forming the coating is injected into the new cavity (envelope construction).

1. a) Formen eines Substrats in einer ersten Kavität des Formwerkzeugs,
2. b) das Einbringen des im vorangegangenen Schritt hergestellten Substrats in eine zweite Kavität des Formwerkzeugs und
3. c) Beschichten des Substrats in der zweiten Kavität mit einem Lack, wobei das Beschichten unter erhöhtem Druck erfolgt.

For example, describes WO 2006/072366 A1 a method of forming and coating a substrate in a mold having at least two cavities. The method comprises the steps:

1. a) forming a substrate in a first cavity of the mold,
2. b) introducing the substrate produced in the previous step into a second cavity of the mold and
3. c) coating the substrate in the second cavity with a lacquer, wherein the coating is carried out under elevated pressure.

Exemplary and preferred are polyurethane coatings and PC / ABS substrates (polycarbonate / acrylonitrile-butadiene-styrene substrates). With regard to a special design of the layers to improve the adhesive properties of the composite material in this application no indications are given.

DE 10 2006 033 059 A1 discloses a method for producing plastic interior parts. Here, in a first step, the carrier is formed in a first tool, wherein the first tool is at least partially replaced by a second tool and then in a second step, the cover layer is formed on the carrier. In this case, the carrier material used is a hard component, for example polyamide / ABS blends or polycarbonate / ABS blends, and a soft component, preferably polyurethane foam, is used as cover layer. to Improvement of adhesion is proposed to prepare the surface by primer or laser, corona or plasma treatment.

A disadvantage of this conventional process is that the coating often does not adhere firmly to the carrier at every point, so that damage to the coating can occur, in particular when the tool is loosened.

1. a) Herstellen eines Trägerbauteils,
2. b) Verbringen oder Umsetzen des Trägerbauteils in eine geöffnete Kavität eines Werkzeugs,
3. c) Schließen des Werkzeugs bis auf eine vorbestimmte Position, wobei eine vergrößerte Kavität mit einer ersten Größe geschaffen ist,
4. d) Erzeugen eines Unterdrucks in der vergrößerten Kavität erster Größe,
5. e) Einfüllen eines Flutungsmaterials in die vergrößerte Kavität und
6. f) Durchführen eines Prägeschrittes gleichzeitig mit dem Einfüllen und/oder anschließend an das Einfüllen des Flutungsmaterials, wobei die Kavität zumindest geringfügig verkleinert wird.

DE 10 2006 048 252 B3 discloses a method for producing a composite component, in particular comprising an injection-molded part and a polyurethane element, with the steps:

1. a) producing a carrier component,
2. b) moving or transferring the carrier component into an opened cavity of a tool,
3. c) closing the tool to a predetermined position creating an enlarged cavity of a first size,
4. d) generating a negative pressure in the enlarged first size cavity,
5. e) filling a flooding material in the enlarged cavity and
6. f) performing an embossing step simultaneously with the filling and / or subsequent to the filling of the flooding material, wherein the cavity is at least slightly reduced.

To improve the bond adhesion, an activation of the surface of the thermoplastic by flaming, plasma or gas is described here.

In contrast to the structuring according to the invention, the activation of a surface serves for adjusting the surface tension and cleaning or improved wetting of a surface. This is done at the molecular level. No macroscopic structures are introduced which result in a targeted increase in the bond strength, as in the present invention.

Further attempts have been made to improve the adhesion between the layers of a composite component. The WO 99/20464 A1 For example, describes a composite of at least two different directly interconnected plastic materials, one of which is a thermoplastic polymer or a mixture of thermoplastic polymers and the other is a polyurethane, wherein the thermoplastic layer is a polar compound of at least one of the metals of the 1st to 5th Main group or the 1st to 8th subgroup of the Periodic table as finely divided inorganic powder, for example, an oxide, sulfate, sulfite, carbonate, hydroxide, carbide, nitrate, nitrite, nitride, borate, silicate, phosphate, hydride, phosphite or phosphonate. The introduction of such powders occurs in the production of the thermoplastic material. The introduction of the powders has an effect on the properties of the thermoplastic, for example the mechanical properties.

It was now an object to optimize the adhesion between directly in contact thermoplastic carrier and coating in order to minimize the waste in the composite parts, to improve the quality of the composite parts and to avoid that coating residues remain attached to the tool.

1. (i) Einspritzen der Schmelze der thermoplastischen Zusammensetzung in eine erste Werkzeugkavität zur Herstellung des thermoplastischen Trägers,
2. (ii) Abkühlen der Schmelze,
3. (iii) Vergrößerung der Kavität des Spritzgusswerkzeugs zur Erzeugung eines Spaltraumes,
4. (iv) Einspritzen eines Rohstoffgemisches zur Formung der zweiten Schicht in diesen Spaltraum zwischen dem thermoplastischen Träger und der Werkzeugoberfläche, wobei das Rohstoffgemisch zur Formung der zweiten Schicht im direkten Kontakt mit der Oberfläche des thermoplastischen Trägers auspolymerisiert,
5. (v) Entformung des Verbundteils aus der Werkzeugkavität,

dadurch gekennzeichnet, dass das Werkzeug, in welches die thermoplastische Zusammensetzung eingespritzt wird, auf seiner inneren Oberfläche eine von einer glatten Oberfläche abweichende Struktur aufweist, durch welche die Oberfläche des thermoplastischen Trägers eine Struktur erhält.The object is achieved according to the invention by a method for producing a composite component according to the invention, comprising a carrier of a thermoplastic composition and a second layer on the carrier, wherein the surface of the carrier adjoining the second layer is structured, the method comprising the following steps, which follow each other in this order:

1. (i) injecting the melt of the thermoplastic composition into a first mold cavity for the production of the thermoplastic carrier,
2. (ii) cooling the melt,
3. (iii) enlarging the cavity of the injection molding tool to produce a gap space,
4. (iv) injecting a mixture of raw materials to form the second layer in said gap space between the thermoplastic carrier and the tool surface, wherein the raw material mixture polymerizes to form the second layer in direct contact with the surface of the thermoplastic carrier,
5. (v) demolding the composite part from the tool cavity,

characterized in that the tool into which the thermoplastic composition is injected has, on its inner surface, a structure deviating from a smooth surface, by which the surface of the thermoplastic carrier obtains a structure.

By "structuring" is meant according to the invention that the support of the composite component, the layer of thermoplastic material, a structure is imparted by the smooth Surface structure, as it results by injection molding with a tool with a smooth surface towards the cavity, deviates. A corresponding "structure" can have different structural depths, ie it can be impressed at different depths into the carrier. Also, the distances between the structural elements, such as the points vary. A structure in the surface of the carrier is preferably achieved according to the invention by providing the tool, in which the carrier is produced by injection molding, with a corresponding negative mold. This is preferably done by the tool, in particular a made of ceramic tool insert or a tool with a ceramic surface, is embossed before curing with a structured element. An embossing can for example be made with a corresponding mask to form a dot pattern or a diamond pattern or with elements such as sandpaper, files, textile materials. The tool can also be provided with a corresponding structure by subsequently a structure is introduced by eroding. Although these are preferred embodiments for providing the necessary structuring element to the tool, the invention should not be so limited. It is only important that the tool used has a corresponding structure, which can also be achieved by other methods, such as lasers. The structure is then imaged on the surface of the thermoplastic carrier.

By "raw material mixture" in process step (iv) is meant those combinations of ingredients which are used to form the second layer, i. in particular for the formation of a polyurethane hardcoat, polyurethane-soft paint, a polyurethane skin or a polyurethane foam, that is, the foam used for the filling of the composite element may be predominantly open-cell or closed-cell and contain a variety of fillers. For foaming, chemical or physical blowing agents can be used. Suitable polymers for the preparation of such core layers may be isocyanate-based (polyurethane, polyurea, polyisocyanurate, polyoxazolidinone, polycarbodiimide), epoxy-based, phenol-based, melamine-based, PVC, polyimide, polyamide or mixtures of said polymers, with thermosets being preferred and isocyanate-based Duromers and their mixtures are particularly preferred.

To increase the cavity in process step (iii), the injection mold can be opened and subsequently one half of the injection mold cavity replaced by a new half with larger cavity dimensions. However, it is also possible for the support to be converted from the first tool cavity into a second cavity of the same or a second tool that is larger in terms of its hollow shape dimensions, or else the first cavity to be opened by a gap.

If the carrier is reacted, this can be done by known methods, as used for example in multi-color injection molding. Typical methods are on the one hand the turntable, insert, Schiebekavität or index plate or similar methods in which the substrate remains on a core. If the substrate remains to be transferred on the core, this has the advantage that the position is defined accurately even after transfer. On the other hand, known in the art are methods of reacting a substrate in which the substrate, e.g. with the help of a handling system, removed from a cavity and placed in another cavity. The transfer with removal of the substrate offers greater latitude in the coating, e.g. when generating a wrap around or masked areas.

Although, according to the invention, preferably a coating and thus also a preceding structuring takes place directly in the injection molding plant with an enlarged cavity, composite parts according to the invention are also those in which the carriers made of thermoplastic material have received a structured surface in a more complicated way by subsequently processing the plastic body, eg by laser, subsequent melting with imprinting of a structure or scoring of a structure. The application of the second layer is then preferably carried out by the flooding of the structured plastic body in a closed or open tool, but can also be done by means of spraying, flooding without tools or other application methods of reactive systems. The inventive method for producing the composite components with the immediate sequence of the reaction steps in one place prevents the temperature of the workpiece from cooling to room temperature during the process. This achieves a reduction of the production times and a higher energy efficiency of the overall process.

Before demoulding the workpiece, the workpiece is cooled to dimensional stability.

An increased mold temperature during the production of the plastic body leads to an improved molding of the structures, but is not absolutely necessary for the structures according to the invention. The increased tool temperature can be made variable in terms of cycle, as is the case in known methods, e.g. variothermic temperature control by means of water, steam, or induction is possible.

When polycarbonate is used as a carrier material, the mold temperature is preferably 80 to 130 ° C, with a polycarbonate blend preferably 60 to 100 ° C.

Preferred structures according to the invention are EDM structures, dot patterns, diamond patterns, textile structures, such as those obtained, for example, by molding textiles, for example Microfibre cloths, sandpaper structures and file structures, particularly preferably dot patterns, textile structures, sandpaper structures and file structures, very particularly preferably textile structures, sandpaper structures and file structures.

For dot screens and diamond screens, it is more preferable to have such structures having a greater texture depth, i. a dot pattern with a pattern depth of 250 μm is more preferred than a dot pattern with a pattern depth of 150 μm, which is more preferable than a dot pattern with a pattern depth of 85 μm. For diamond grids, for example, a diamond pattern with a pattern depth of 250 μm is more preferred than a diamond pattern with a pattern depth of 150 μm, which in turn is more preferred than a diamond pattern with a pattern depth of 70 μm.

By the "surface of the carrier adjacent to the second layer" is meant, according to the invention, the surface which is in contact with the second layer, e.g. a coating, such as a paint is. This may be a single side of the carrier, but also its entire surface when the carrier is completely enclosed with a second layer. Likewise, only a limited area of one side of the carrier may have a structure and be provided there with a second layer.

According to the invention can be used as a material for the carrier each thermoplastic or a mixture of different thermoplastics.

The thermoplastic used is preferably a polycarbonate, a polystyrene, a styrene copolymer, for example transparent polystyrene acrylonitrile (PSAN), an aromatic polyester, for example polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, or another polyalkylene terephthalate, a polyolefin, such as a polypropylene or a polyethylene, a polyacrylate or copolyacrylate, a polymethacrylate or copolymer methacrylate, for example poly- or copolymethyl methacrylate, a polyamide, a styrene-acrylonitrile copolymer, a thermoplastic polyurethane, a polymer based on cyclic olefins or a mixture of the polymers mentioned.

The thermoplastics generally contain conventional additives such as mold release agents, heat stabilizers, UV absorbers, but also flame retardants, IR absorbers, antistatic agents, colorants, etc. may be included.

Particular preference is given to the thermoplastics selected from the group consisting of polycarbonates (homopolymers or copolycarbonates) and also polycarbonate blends, for example polycarbonate / polyester blends or polycarbonate / ABS blends (ABS: acrylonitrile-butadiene-styrene copolymer) or blends with styrene / acrylonitrile copolymers (SAN). Preferred polycarbonate / polyester blends are mixtures of polycarbonate with polyalkylene terephthalate (in particular with polybutylene terephthalate). The proportion of the polyalkylene terephthalate is generally from 5 to 95 wt .-%, preferably 10 to 70 wt .-%, in particular 30 to 60 wt .-%, based on the total composition of the thermoplastic carrier.

Polycarbonates in the context of the present invention are both homopolycarbonates, copolycarbonates and polyestercarbonates as described, for example, in US Pat EP 1 657 281 A1 are described. Suitable aromatic polycarbonates and polyester carbonates, for example, are known from the literature or can be prepared by processes known from the literature (for the preparation of aromatic polycarbonates, see, for example, Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, 1964, and US Pat DE 1 495 626 B1 . DE 2 232 877 A1 . DE 2 703 376 A1 . DE 2 714 544 A1 . DE 3 000 610 A1 . DE 3 832 396 A1 ; for the preparation of aromatic polycarbonates see, for example DE 3 007 934 A1 ). For the preparation of copolycarbonates, it is also possible to use from 1 to 25% by weight, preferably from 2.5 to 25% by weight, based on the total amount of diphenols to be used, of hydroxyaryloxy endblocked polydiorganosiloxanes. These are known ( US 3 419 634 A ) and produced by literature methods. The preparation of polydiorganosiloxane-containing copolycarbonates is in the DE 3 334 782 A1 described.

The preparation of aromatic polycarbonates z. Example, by reacting diphenols with carbonic acid halides, preferably phosgene and / or with aromatic dicarboxylic acid dihalides, preferably Benzoldicarbonsäuredihalogeniden, by the interfacial process, optionally using chain terminators, for example monophenols, and optionally using trifunctional or more than trifunctional branching agents, for example triphenols or tetraphenols , Likewise, preparation via a melt polymerization process by reaction of diphenols with, for example, diphenyl carbonate is possible.

wobei

A

eine Einfachbindung, C₁- bis C₅-Alkylen, C₂- bis C₅-Alkyliden, C₅- bis C₆-Cycloalkyliden, -O-, -SO-, -CO-, -S-, -SO₂-, C₆ bis C₁₂-Arylen, an das weitere aromatische gegebenenfalls Heteroatome enthaltende Ringe kondensiert sein können, oder ein Rest der Formel (II) oder (III)

B

jeweils C₁- bis C₁₂-Alkyl, vorzugsweise Methyl, Halogen, vorzugsweise Chlor und/oder Brom,

x

jeweils unabhängig voneinander 0, 1 oder 2,

p

1 oder 0 sind, und

R⁵ und R⁶

für jedes X¹ individuell wählbar, unabhängig voneinander Wasserstoff oder C₁- bis C₆-Alkyl, vorzugsweise Wasserstoff, Methyl oder Ethyl,

X¹

Kohlenstoff und

m

eine ganze Zahl von 4 bis 7, bevorzugt 4 oder 5 bedeuten, mit der Maßgabe, dass an mindestens einem Atom X¹, R⁵ und R⁶ gleichzeitig Alkyl sind.

Diphenols for the preparation of the aromatic polycarbonates and / or aromatic polyester carbonates are preferably those of the formula (I)

in which

A

a single bond, C ₁ - to C ₅ -alkylene, C ₂ - to C ₅ -alkylidene, C ₅ - to C ₆ -cycloalkylidene, -O-, -SO-, -CO-, -S-, -SO ₂ - , C ₆ to C ₁₂ -aryl, to which further aromatic rings containing optionally heteroatoms may be condensed, or a radical of the formula (II) or (III)

B

in each case C ₁ - to C ₁₂ -alkyl, preferably methyl, halogen, preferably chlorine and / or bromine,

x

each independently 0, 1 or 2,

p

1 or 0 are, and

R ⁵ and R ⁶

individually selectable for each X ¹ , independently of one another hydrogen or C ₁ - to C ₆ -alkyl, preferably hydrogen, methyl or ethyl,

X ¹

Carbon and

m

an integer from 4 to 7, preferably 4 or 5, with the proviso that on at least one atom X ¹ , R ⁵ and R ^{6 are} simultaneously alkyl.

Preferred diphenols are hydroquinone, resorcinol, dihydroxydiphenols, bis (hydroxyphenyl) -C _{1 to} C ₅ alkanes, bis (hydroxyphenyl) C ₅ or C ₆ cycloalkanes, bis (hydroxyphenyl) ethers, bis - (hydroxyphenyl) sulfoxides, bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfones and α, α-bis (hydroxyphenyl) diisopropylbenzenes and their nuclear-brominated and / or nuclear-chlorinated derivatives.

Particularly preferred diphenols are 4,4'-dihydroxydiphenyl, bisphenol-A, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxyphenyl) -cyclohexane, 1,1- Bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxydiphenylsulfone and their di- and tetrabrominated or chlorinated derivatives such as 2,2-bis (3-chloro-4 -hydroxyphenyl) -propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) -propane or 2,2-bis (3,5-dibromo-4-hydroxyphenyl) -propane. Particularly preferred is 2,2-bis (4-hydroxyphenyl) propane (bisphenol-A).

The diphenols can be used individually or as any mixtures. The diphenols are known from the literature or obtainable by literature methods.

Chain terminators suitable for the preparation of the thermoplastic, aromatic polycarbonates are, for example, phenol, p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol, but also long-chain alkylphenols, such as 4- [2- (2,4,4 -Trimethylpentyl)] - phenol, 4- (1,3-tetramethylbutyl) phenol according to DE-A 2 842 005 or monoalkylphenols or dialkylphenols having a total of 8 to 20 carbon atoms in the alkyl substituents, such as 3,5-di-tert-butylphenol, p-iso-octylphenol, p-tert-octylphenol, p-dodecylphenol and 2- (3,5- Dimethylheptyl) phenol and 4- (3,5-dimethylheptyl) phenol. The amount of chain terminators to be used is generally between 0.5 mol% and 10 mol%, based on the molar sum of the diphenols used in each case.

The polycarbonates may be linear or branched. It is also possible to use mixtures of branched and unbranched polycarbonates. Suitable branching agents for polycarbonates are known from the literature and described for example in the patents US-A 4,185,009 and DE 25 00 092 A1 (Inventive 3,3-bis- (4-hydroxyaryl-oxindoles, see in each case entire document), DE 42 40 313 A1 (see page 3, lines 33 to 55), DE 19 943 642 A1 (see page 5, lines 25 to 34) and US Pat. No. 5,367,044 as well as in literature cited herein. Branches, preferably trifunctional compounds or compounds having even more functions, for example those having three or more phenolic OH groups, are preferably incorporated in amounts of from 0.05 to 2.0 mol%, based on the total amount of diphenols to be used. In addition, the polycarbonates used can also be intrinsically branched, in which case no branching agent is added during the polycarbonate production. An example of intrinsic branching are so-called frieze structures, as used for melt polycarbonates in the EP 1 506 249 A1 are disclosed.

Preferred polycarbonates, in addition to the bisphenol A homopolycarbonates, are the copolycarbonates of bisphenol A with up to 15 mol%, based on the molar sums of diphenols, other than Preferred or particularly preferred diphenols, in particular 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane.

In addition, chain terminators can be used in polycarbonate production. The chain terminators used are preferably phenols such as phenol, alkylphenols such as cresol and 4-tert-butylphenol, chlorophenol, bromophenol, cumylphenol or mixtures thereof.

Aromatic dicarboxylic acid dihalides for the preparation of aromatic polyester carbonates are preferably the diacid dichlorides of isophthalic acid, terephthalic acid, diphenyl ether-4,4'-dicarboxylic acid and naphthalene-2,6-dicarboxylic acid. Particularly preferred are mixtures of the diacid dichlorides of isophthalic acid and terephthalic acid in the ratio between 1:20 and 20: 1.

In the production of polyester carbonates, a carbonyl halide, preferably phosgene, is additionally used as bifunctional acid derivative.

As chain terminators for the preparation of the aromatic polyester, in addition to the aforementioned monophenols still their chlorocarbonic acid esters and the acid chlorides of aromatic monocarboxylic acids, which may be substituted by C ₁ - to C ₂₂ alkyl groups or by halogen atoms, and aliphatic C ₂ - to C ₂₂ -Monocarbonsäurechloride into consideration.

The amount of chain terminators is in each case 0.1 to 10 mol%, based on moles of diphenol in the case of the phenolic chain terminators and on moles of dicarboxylic acid dichloride in the case of monocarboxylic acid chloride chain terminators.

The aromatic polyester carbonates may also contain incorporated aromatic hydroxycarboxylic acids.

The aromatic polyester carbonates can be branched both linearly and in a known manner (see DE 2 940 024 A1 and DE 3 007 934 A1 ).

Examples of branching agents which may be used are trifunctional or polyfunctional carboxylic acid chlorides, such as trimesic acid trichloride, cyanuric trichloride, 3,3 ', 4,4'-benzophenone tetracarboxylic acid tetrachloride, 1,4,5,8-naphthalene tetracarboxylic acid tetrachloride or pyromellitic acid tetrachloride, in amounts of 0 , 01 to 1.0 mol% (based on the dicarboxylic acid dichlorides used) or difunctional or polyfunctional phenols, such as phloroglucinol, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hept-2-ene, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tri (4-hydroxyphenyl) benzene, 1,1,1-tri- (4-hydroxyphenyl ) ethane, tri- (4-hydroxyphenyl) -phenylmethane, 2,2-bis [4,4-bis (4-hydroxyphenyl) -cyclohexyl] -propane, 2,4-bis (4-hydroxyphenyl-isopropyl) -phenol, tetra (4-hydroxyphenyl) -methane, 2,6-bis (2-hydroxy-5-methyl-benzyl) -4-methyl-phenol, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) -propane, tetra (4- [4-hydroxyphenyl-isopropyl] -phenoxy) -methane, 1,4-bis [4,4'-dihydroxytriphenyl ) -methyl] -benzene, in amounts of from 0.01 to 1.0 mol%, based on the diphenols used. Phenolic branching agents can be introduced with the diphenols, acid chloride branching agents can be added together with the acid dichlorides.

In the thermoplastic, aromatic polyester carbonates, the proportion of carbonate structural units can vary as desired. The proportion of carbonate groups is preferably up to 100 mol%, in particular up to 80 mol%, particularly preferably up to 50 mol%, based on the sum of ester groups and carbonate groups. Both the ester and the carbonate portion of the aromatic polyester carbonates may be present in the form of blocks or randomly distributed in the polycondensate.

The relative solution viscosity (η _rel ) of the aromatic polycarbonates and polyester carbonates for the preparation of the composition is in the range of 1.18 to 1.4, preferably 1.20 to 1.32, particularly preferably 1.24 to 1.30 (measured on solutions of 0.5 g of polycarbonate or polyester carbonate in 100 ml of methylene chloride solution at 25 ° C).

The weight-average molecular weight M _{w of} the thermoplastic aromatic polycarbonates and the polyestercarbonates is preferably in the range of 15,000 to 50,000 g / mol, more preferably in the range of 15,000 to 35,000 g / mol, still more preferably in the range of 20,000 to 33,000 g / mol preferably in the range 23,000 to 30,000 g / mol, determined by GPC (gel permeation chromatography in methylene chloride with polycarbonate as standard).

According to the invention, by "coating" is meant a layer which is applied to the carrier, wherein the carrier may have any shape and should not be understood to be limited to (nearly) plate-like shapes.

Suitable materials for the formation of the second layer according to the invention are hard and soft coatings and foams, preferably polyurethane coatings, both hard and soft coatings, and polyurethane foams, particularly preferably hard coatings, in question. Also polyurethane skins can be used as second layer.

Preferably, the raw material mixture for forming the second layer contains at least one polyisocyanate component, at least one H-active compound and optionally at least one polyurethane additive and / or processing aid, wherein the second layer by polymerization this reactive polyurethane raw material mixture is made in direct contact with the carrier previously formed and solidified from the thermoplastic composition.

According to the invention, the term "polyurethane" is also understood to mean polyurethaneureas in which H-active polyfunctional compounds such compounds having N-H functionality, if appropriate in admixture with polyols, are used.

The coating used is preferably a polyurethane foam or a compact polyurethane layer.

The polyurethanes used according to the invention are obtained by reacting polyisocyanates with H-active polyfunctional compounds, preferably polyols.

In the context of this invention, the term "polyurethane" is also understood as meaning polyurethaneureas in which H-active polyfunctional compounds such compounds having N-H functionality, if appropriate in admixture with polyols, are used.

Suitable polyisocyanates are the aromatic, araliphatic, aliphatic or cycloaliphatic polyisocyanates having an NCO functionality of preferably ≥ 2 which are known per se to the person skilled in the art and which also include iminooxadiazinedione, isocyanurate, uretdione, urethane, allophanate, biuret, urea, oxadiazinetrione , Oxazolidinone, acylurea and / or carbodiimide structures. These can be used individually or in any mixtures with each other.

The abovementioned polyisocyanates are based on diisocyanates or triisocyanates known per se with aliphatic, cycloaliphatic, araliphatic and / or aromatically bound isocyanate groups, it being immaterial whether these were prepared by using phosgene or by phosgene-free processes. Examples of such di- or triisocyanates are 1,4-diisocyanatobutane, 1,5-diisocyanatopentane, 1,6-diisocyanatohexane (HDI), 2-methyl-1,5-diisocyanatopentane, 1,5-diisocyanato-2,2- dimethylpentane, 2,2,4- and 2,4,4-trimethyl-1,6-diisocyanatohexane, 1,10-diisocyanatodecane, 1,3- and 1,4-diisocyanatocyclohexane, 1,3- and 1,4- bis- (isocyanatomethyl) -cyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl cyclohexane (isophorone diisocyanate, IPDI), 4,4'-diisocyanatodicyclohexylmethane (Desmodur ^® W, Bayer AG, Leverkusen, DE), 4- Isocyanatomethyl-1,8-octane diisocyanate (triisocyanatononane, TIN), ω, ω'-diisocyanato-1,3-dimethylcyclohexane (H ₆ XDI), 1-isocyanato-1-methyl-3-isocyanato-methylcyclohexane, 1-isocyanato-1 -methyl-4-isocyanato-methylcyclohexane, bis (isocyanatomethyl) -norboman, 1,5-naphthalene diisocyanate, 1,3- and 1,4-bis (2-isocyanato-prop-2-yl) -benzene ( TMXDI), 2,4- and 2,6-diisocyanatotoluene (TDI), in particular the 2,4- and 2,6-isomers and technical mixtures of the two isomers, 2,4'- and 4,4'-diisocyanatodiphenylmethane (MDI), polymeric MDI (pMDI) 1 , 5-diisocyanatonaphthalene, 1,3-bis (isocyanato-methyl) benzene (XDI) and any mixtures of said compounds.

The polyisocyanates preferably have an average NCO functionality of from 2.0 to 5.0, preferably from 2.2 to 4.5, particularly preferably from 2.2 to 2.7, and a content of isocyanate groups of from 5.0 to 37 , 0 wt .-%, preferably from 14.0 to 34.0 wt .-% to.

In a preferred embodiment, polyisocyanates or polyisocyanate mixtures of the abovementioned type with exclusively aliphatically and / or cycloaliphatically bonded isocyanate groups are used.

The polyisocyanates of the abovementioned type are very particularly preferably based on hexamethylene diisocyanate, isophorone diisocyanate, the isomeric bis (4,4'-isocyanatocyclohexyl) methanes and mixtures thereof.

Among the higher molecular weight, modified polyisocyanates are in particular the known from polyurethane chemistry prepolymers having terminal isocyanate groups in the molecular weight range 400 to 15,000 g / mol, preferably 600 to 12,000 g / mol of interest. These compounds are prepared in a conventional manner by reacting excess amounts of simple polyisocyanates of the type exemplified with organic compounds having at least two isocyanate-reactive groups, in particular organic polyhydroxyl compounds. Suitable such polyhydroxyl compounds are both simple polyhydric alcohols of the molecular weight range 62 to 599 g / mol, preferably 62 to 200 g / mol, such as ethylene glycol, trimethylolpropane, 1,2-propanediol or 1,4-butanediol or 2,3-butanediol, in particular however, higher molecular weight polyether polyols and / or polyester polyols known in polyurethane chemistry with molecular weights of 600 to 12,000 g / mol, preferably 800 to 4,000 g / mol, the at least two, usually 2 to 8, but preferably 2 to 6 primary and / or having secondary hydroxyl groups. Of course, it is also possible to use those NCO prepolymers which have been obtained, for example, from low molecular weight polyisocyanates of the type mentioned by way of example and less preferred compounds having isocyanate-reactive groups such as polythioether polyols, hydroxyl-containing polyacetals, polyhydroxypolycarbonates, polyesteramides containing hydroxyl groups or copolymers of olefinically unsaturated compounds having hydroxyl groups are.

For the preparation of NCO prepolymers suitable compounds having isocyanate-reactive groups, in particular hydroxyl groups, for example, in the US Pat. No. 4,218,543 disclosed compounds. In the preparation of the NCO prepolymers, these compounds are reacted with isocyanate-reactive groups with simple polyisocyanates of the type exemplified above while maintaining an NCO excess. The NCO prepolymers generally have an NCO content of 10 to 26 wt .-%, preferably 15 to 26 wt .-% to. From this it is already apparent that in the context of the present invention under "NCO prepolymers" or "prepolymers with terminal isocyanate groups" both the reaction products as such and the mixtures with excess amounts of unreacted starting polyisocyanates, which are often also called "semiprepolymers" are meant to be understood.

Suitable aliphatic diols having an OH number of> 500 mg KOH / g are the chain extenders customarily used in polyurethane chemistry, such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-propanediol. Preference is given to diols such as 1,4-butanediol, 2-butenediol-1,3, butanediol-2,3 and / or 2-methylpropanediol-1,3. Of course, it is also possible to use the aliphatic diols in a mixture with each other.

Polyols having an average OH number of from 5 to 600 mg KOH / g and an average functionality of from 2 to 6 are suitable as the H-active component. Polyols having an average OH number of from 10 to 50 mg KOH / g are preferred. Polyols suitable according to the invention are, for example, polyhydroxypolyethers obtainable by alkoxylation of suitable starter molecules such as ethylene glycol, diethylene glycol, 1,4-dihydroxybutane, 1,6-dihydroxyhexane, dimethylolpropane, glycerol, pentaerythritol, sorbitol or sucrose. Also suitable as initiators are ammonia or amines such as ethylenediamine, hexamethylenediamine, 2,4-diaminotoluene, aniline or amino alcohols or phenols such as bisphenol-A. The alkoxylation is carried out using propylene oxide and / or ethylene oxide in any order or as a mixture.

In addition to polyols, it is additionally possible to comprise at least one further crosslinker and / or chain extender selected from the group comprising amines and amino alcohols, for example ethanolamine, diethanolamine, diisopropanolamine, ethylenediamine, triethanolamine, isophoronediamine, N, N'-dimethyl (diethyl) -ethylenediamine, 2-Amino-2-methyl (or ethyl) -1-propanol, 2-amino-1-butanol, 3-amino-1,2-propanediol, 2-amino-2-methyl (ethyl) -1,3-propanediol , and alcohols, for example, ethylene glycol, diethylene glycol, 1,4-dihydroxybutane, 1,6-dihydroxyhexane, dimethylolpropane, glycerol and pentaerythritol, as well as sorbitol and sucrose, or mixtures of these compounds.

Also suitable are polyester polyols, as they are accessible by reacting low molecular weight alcohols with polybasic carboxylic acids such as adipic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid or the anhydrides of these acids in a conventional manner, provided that the viscosity of the H-active component is not too large. A preferred polyol having ester groups is castor oil. In addition, there are also preparations with castor oil, such as those obtained by dissolving resins, e.g. of aldehyde-ketone resins, as well as modifications of castor oil and polyols based on other natural oils.

Also suitable are those relatively high molecular weight polyhydroxypolyethers in which high molecular weight polyadducts or polycondensates or polymers in finely dispersed, dissolved or grafted form are present. Such modified polyhydroxy compounds are prepared in a manner known per se, e.g. when polyaddition reactions (e.g., reactions between polyisocyanates and aminofunctional compounds) and polycondensation reactions (e.g., between formaldehyde and phenols and / or amines) occur in situ in the hydroxyl group-containing compounds. However, it is also possible to mix a finished aqueous polymer dispersion with a polyhydroxyl compound and then to remove the water from the mixture.

Vinyl polymer-modified polyhydroxyl compounds, as obtained, for example, by polymerization of styrene and acrylonitrile in the presence of polyethers or polycarbonate polyols, are also suitable for the preparation of polyurethanes. When using polyether polyols, which according to DE-A 2 442 101 . DE-A 2 844 922 and DE-A 2 646 141 By graft polymerization with vinylphosphonic and optionally (meth) acrylonitrile, (meth) acrylamide or OH-functional (meth) acrylic acid esters were modified to obtain plastics of particular flame retardancy.

Representatives of the mentioned, to be used as H-active compounds compounds are, for example in High Polymers, Vol. XVI, "Polyurethanes Chemistry and Technology", Saunders-Frisch (Ed.) Interscience Publishers, New York, London, Vol. 1, pp. 32-42, 44, 54 and Vol. II, 1984, pp. 5-6 and pp. 198-199 described.

It is also possible to use mixtures of the compounds listed.

The limitation of the average OH number and average functionality of the H-active component results in particular from the increasing embrittlement of the resulting polyurethane. In principle, however, the person skilled in the influence on the polymer-physical properties of the polyurethane are known, so that NCO component, aliphatic diol and polyol can be suitably matched to each other.

The polyurethane layer (b) may be foamed or solid, e.g. present as a paint or coating. For their preparation, all known auxiliaries and additives, such as. Release agents, blowing agents, fillers, catalysts and flame retardants are used.

1. a) Wasser und/oder leicht flüchtige anorganische oder organische Substanzen als Treibmittel
   Als organische Treibmittel kommen z.B. Aceton, Ethylacetat, halogensubstituierte Alkane wie Methylenchlorid, Chloroform, Ethylidenchlorid, Vinylidenchlorid, Monofluortrichlormethan, Chlordifluormethan, Dichlordifluormethan, ferner Butan, Hexan, Heptan oder Diethylether, als anorganische Treibmittel Luft, CO₂ oder N₂O in Frage. Eine Treibwirkung kann auch durch Zusatz von sich bei Temperaturen über Raumtemperatur unter Abspaltung von Gasen, beispielsweise von Stickstoff, zersetzenden Verbindungen, z.B. Azoverbindungen wie Azodicarbonamid oder Azoisobuttersäurenitril, erzielt werden.
2. b) Katalysatoren
   Bei den Katalysatoren handelt sich beispielsweise um
   tertiäre Amine (wie Triethylamin, Tributylamin, N-Methylmorpholin, N-Ethylmorpholin, N,N,N',N'-Tetramethylethylendiamin, Pentamethyldiethylentriamin und höhere Homologe, 1,4-Diazabicyclo-(2,2,2)octan, N-Methyl-N'-dimethylaminoethylpiperazin, Bis-(dimethylaminoalkyl)piperazine, N,N-Dimethylbenzylamin, N,N-Dimethylcyclohexylamin, N,N-Diethylbenzylamin, Bis-(N,N-diethylamino-ethyl)adipat, N,N,N',N'-Tetramethyl-1,3-butandiamin, N,N-Dimethyl-β-phenylethylamin, 1,2-Dimethylimidazol, 2-Methylimidazol),
   monocyclische und bicyclische Amide, Bis-(dialkylamino)alkylether,
   Amidgruppen (vorzugsweise Formamidgruppen) aufweisende tertiäre Amine,
   Mannichbasen aus sekundären Aminen (wie Dimethylamin) und Aldehyden, (vorzugsweise Formaldehyd oder Ketonen wie Aceton, Methylethylketon oder Cyclohexanon) und Phenolen (wie Phenol, Nonylphenol oder Bisphenol),
   gegenüber Isocyanatgruppen aktive Wasserstoffatome aufweisende tertiäre Amine (z.B. Triethanolamin, Triisopropanolamin, N-Methyldiethanolamin, N-Ethyldietanolamin, N,N-Dimethylethanolamin), sowie deren Umsetzungsprodukte mit Alkylenoxiden wie Propylenoxid und/oder Ethylenoxid,
   sekundäre Amine, tertiäre Amine,
   Silaamine mit Kohlenstoff-Silicium-Bindungen (2,2,4-Trimethyl-2-silamorpholin und 1,3-Diethylaminomethyltetramethyldisiloxan),
   stickstoffhaltige Basen (wie Tetraalkylammoniumhydroxide), Alkalihydroxide (wie Natriumhydroxid, Alkaliphenolate wie Natriumphenolat),
   Alkalialkoholate (wie Natriummethylat), und/oder
   Hexahydrotriazine.

If necessary as auxiliaries and admixtures are to be used:

1. a) water and / or volatile inorganic or organic substances as blowing agent
   Suitable organic blowing agents are, for example, acetone, ethyl acetate, halogen-substituted alkanes such as methylene chloride, chloroform, ethylidene chloride, vinylidene chloride, monofluorotrichloromethane, chlorodifluoromethane, dichlorodifluoromethane, furthermore butane, hexane, heptane or diethyl ether, as inorganic blowing agents air, CO ₂ or N ₂ O in question. A blowing effect can also be achieved by addition of itself at temperatures above room temperature with elimination of gases, for example nitrogen, decomposing compounds, eg azo compounds such as azodicarbonamide or azoisobutyronitrile.
2. b) catalysts
   The catalysts are, for example, to
   tertiary amines (such as triethylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, N, N, N ', N'-tetramethylethylenediamine, pentamethyldiethylenetriamine and higher homologs, 1,4-diazabicyclo- (2,2,2) octane, N- Methyl-N'-dimethylaminoethylpiperazine, bis (dimethylaminoalkyl) piperazine, N, N-dimethylbenzylamine, N, N-dimethylcyclohexylamine, N, N-diethylbenzylamine, bis (N, N-diethylamino-ethyl) adipate, N, N, N ', N'-tetramethyl-1,3-butanediamine, N, N-dimethyl-β-phenylethylamine, 1,2-dimethylimidazole, 2-methylimidazole),
   monocyclic and bicyclic amides, bis (dialkylamino) alkyl ethers,
   Amide groups (preferably formamide groups) having tertiary amines,
   Mannich bases of secondary amines (such as dimethylamine) and aldehydes, (preferably formaldehyde or ketones such as acetone, methyl ethyl ketone or cyclohexanone) and phenols (such as phenol, nonylphenol or bisphenol),
   tertiary amines containing isocyanate-active hydrogen atoms (eg triethanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyldietanolamine, N, N-dimethylethanolamine), and their reaction products with alkylene oxides such as propylene oxide and / or ethylene oxide,
   secondary amines, tertiary amines,
   Silaamines having carbon-silicon bonds (2,2,4-trimethyl-2-silamorpholine and 1,3-diethylaminomethyltetramethyldisiloxane),
   nitrogenous bases (such as tetraalkylammonium hydroxides), alkali hydroxides (such as sodium hydroxide, alkali phenolates such as sodium phenolate),
   Alkali alcoholates (such as sodium methylate), and / or
   Methylate.

The reaction between NCO groups and Zerewitinoff-active hydrogen atoms is also greatly accelerated in a manner known per se by lactams and azalactams, initially forming an associate between the lactam and the compound with acidic hydrogen.

It is also possible to use organic metal compounds, in particular organic tin and / or bismuth compounds, as catalysts. Suitable tin compounds in addition to sulfur-containing compounds such as di-n-octyl-tin mercaptide are preferably tin (II) salts of carboxylic acids such as tin (II) acetate, tin (II) octoate, tin (II) ethylhexoate and tin (II). laurate and the tin (IV) compounds, for example dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate or dioctyltin diacetate. Organic bismuth catalysts are described, for example, in the patent application WO 2004/000905 described.

Of course, all the catalysts mentioned above can be used as mixtures. Of particular interest are combinations of organic metal compounds and amidines, aminopyridines or hydrazinopyridines.

• c) Oberflächenaktive Zusatzstoffe wie Emulgatoren und Schaumstabilisatoren
  Als Emulgatoren kommen z.B. die Natriumsalze von Rizinusölsulfonaten oder Salze von Fettsäuren mit Aminen wie ölsaures Diethylamin oder stearinsaures Diethanolamin in Frage. Auch Alkali- oder Ammoniumsalze von Sulfonsäuren wie etwa von Dodecylbenzolsulfonsäure oder Dinaphthylmethandisulfonsäure oder von Fettsäuren wie Rizinolsäure oder von polymeren Fettsäuren können als oberflächenaktive Zusatzstoffe mitverwendet werden.
  Als Schaumstabilisatoren kommen vor allem Polyethersiloxane, speziell wasserlösliche Vertreter, in Frage. Diese Verbindungen sind im Allgemeinen so aufgebaut, dass ein Copolymerisat aus Ethylenoxid und Propylenoxid mit einem Polydimethylsiloxanrest verbunden ist. Von besonderem Interesse sind vielfach über Allophanatgruppen verzweigte Polysiloxan-Polyoxyalkylen-Copolymere.
• d) Reaktionsverzögerer
  Als Reaktionsverzögerer kommen z.B. sauer reagierende Stoffe (wie Salzsäure oder organische Säurehalogenide) in Frage.
• e) Additive
  Als PU-Additive kommen beispielsweise Zellregler der an sich bekannten Art (wie Paraffine oder Fettalkohole) oder Dimethylpolysiloxane sowie Pigmente oder Farbstoffe und Flammschutzmittel der an sich bekannten Art (z.B. Tris-chlorethylphosphat, Trikresylphosphat oder Ammoniumphosphat und -polyphosphat), ferner Stabilisatoren gegen Alterungs- und Witterungseinflüsse, Weichmacher und fungistatisch und bakteriostatisch wirkende Substanzen sowie Füllstoffe (wie Bariumsulfat, Kieselgur, Ruß oder Schlämmkreide) in Betracht.
  Weitere Beispiele von gegebenenfalls erfindungsgemäß mitzuverwendenden oberflächenaktiven Zusatzstoffen und Schaumstabilisatoren sowie Zellreglern, Reaktionsverzögerern, Stabilisatoren, flammhemmenden Substanzen, Weichmachern, Farbstoffen und Füllstoffen sowie fungistatisch und bakteriostatisch wirksamen Substanzen sind dem Fachmann bekannt und in der Literatur beschrieben.

The catalysts are generally used in an amount of about 0.001 to 10 wt .-%, based on the total amount of compounds having at least two isocyanate-reactive hydrogen atoms.

• c) Surface-active additives such as emulsifiers and foam stabilizers
  Suitable emulsifiers are, for example, the sodium salts of castor oil sulfonates or salts of fatty acids with amines such as diethylamine or diethanolamine stearic acid. Also, alkali metal or ammonium salts of sulfonic acids such as dodecylbenzenesulfonic acid or dinaphthylmethanedisulfonic acid or of fatty acids such as ricinoleic acid or of polymeric fatty acids can also be used as surface-active additives.
  Suitable foam stabilizers are in particular polyethersiloxanes, especially water-soluble representatives. These compounds are generally designed so that a copolymer of ethylene oxide and propylene oxide is connected to a Polydimethylsiloxanrest. Of particular interest are branched polysiloxane-polyoxyalkylene copolymers, often via allophanate groups.
• d) reaction retarder
  Suitable reaction inhibitors are, for example, acidic substances (such as hydrochloric acid or organic acid halides).
• e) additives
  Suitable PU additives are, for example, cell regulators of the type known per se (such as paraffins or fatty alcohols) or dimethylpolysiloxanes, and also pigments or dyes and flame retardants of the type known per se (for example tris-chloroethyl phosphate, tricresyl phosphate or ammonium phosphate and polyphosphate), and stabilizers against aging. and weathering agents, plasticizers and fungistatic and bacteriostatic substances and fillers (such as barium sulfate, diatomaceous earth, carbon black or whiting) into account.
  Further examples of optionally used according to the invention surface-active additives and foam stabilizers and cell regulators, reaction retarders, stabilizers, flame retardants, plasticizers, dyes and fillers and fungistatic and bacteriostatic substances are known in the art and described in the literature.

In the case of foamed structures, the layer thickness of the second layer is preferably between 0.5 mm and 40 mm, more preferably between 0.75 mm and 20 mm, particularly preferably between 1 mm and 15 mm.

In the case of compact structures, the layer thickness of the second layer is preferably between 0.05 mm and 10 mm, more preferably between 0.1 mm and 8 mm, particularly preferably between 0.15 mm and 5 mm.

When the thickness of the second layer is on the order of the depth of the grain, the structure on the surface of the carrier partially forms in the second layer. To achieve a smooth surface, another layer can be applied to the second layer.

The composite adhesion between the carrier of thermoplastic, preferably of polycarbonate or polycarbonate blend, and the second layer, preferably a polyurethane coating in the form of a varnish or a foam, in the composite parts according to the invention is preferably at least 0.3 N / mm, more preferably at least 1.0 N / mm, measured on strips taken from the component with a width of 25 mm in a roller peel test according to DIN EN 1464 with a test speed of 100 mm / min.

If foamed composites are to be produced, the reaction mixture can be introduced in a manner known per se into a mold containing the preformed and solidified support. In the mold, the foamable reaction mixture of the second layer foams in contact with the support member and forms the composite member. The foaming of the mold can be carried out in such a way that the composite component has a cell structure on its surface. But it can also be carried out so that the composite component has a compact skin and a cellular core (integral skin foams). Polyurethane foams can also be made as a block foam.

The following are for better understanding based on the FIGS. 1 and 2 the inventive method for producing the composite parts obtainable according to the invention and based on the FIGS. 3 to 28 preferred structures, which can be applied by means of the method on the carrier layer, explained in more detail.

Fig. 1:

das erfindungsgemäße Verfahren zur Herstellung eines Verbundteils;

Fig. 2:

Strukturen auf der Werkzeugoberfläche;

Fig. 3:

Mikroskopiebild: Querschnitt Polyurethan-beschichteter Träger aus Bayblend® T85 SG (Polycarbonat/ABS-Blend) mit Erodierstruktur, VDI 33;

Fig. 4:

Mikroskopiebild: Querschnitt Polyurethan-beschichteter Träger aus Bayblend® T85 SG (Polycarbonat/ABS-Blend) mit Erodierstruktur, VDI 42;

Fig. 5:

Mikroskopiebild: Querschnitt Polyurethan-beschichteter Träger aus Makroblend® UT6405 SG (Polycarbonat/Polyester-Blend) mit Punktstruktur 3a;

Fig. 6:

Mikroskopiebild: Querschnitt Polyurethan-beschichteter Träger aus Makroblend® UT6405 SG (Polycarbonat/Polyester-Blend) mit Punktstruktur 3b;

Fig. 7:

Mikroskopiebild: Querschnitt Polyurethan-beschichteter Träger aus Makroblend® UT6405 SG (Polycarbonat/Polyester-Blend) mit Punktstruktur 3c;

Fig. 8:

Mikroskopiebild: Querschnitt Polyurethan-beschichteter Träger aus Bayblend® T85 SG (Polycarbonat/ABS-Blend) mit Rautenstruktur 4a;

Fig. 9:

Mikroskopiebild: Querschnitt Polyurethan-beschichteter Träger aus Bayblend® T85 SG (Polycarbonat/ABS-Blend) mit Rautenstruktur 4b;

Fig. 10:

Mikroskopiebild: Querschnitt Polyurethan-beschichteter Träger aus Bayblend® T85 SG (Polycarbonat/ABS-Blend) mit Rautenstruktur 4c;

Fig. 11:

Mikroskopiebild: Querschnitt Polyurethan-beschichteter Träger aus Bayblend® T85 SG (Polycarbonat/ABS-Blend) mit Struktur 5a;

Fig. 12:

Mikroskopiebild: Querschnitt Polyurethan-beschichteter Träger aus Bayblend® T85 SG (Polycarbonat/ABS-Blend) mit Struktur 5c;

Fig. 13:

Mikroskopiebild: Querschnitt Polyurethan-beschichteter Träger aus Bayblend® T85 SG (Polycarbonat/ABS-Blend) mit Struktur 5b;

Fig.14:

Mikroskopiebild: Querschnitt Polyurethan-beschichteter Träger aus Makroblend® UT6405 SG (Polycarbonat/Polyester-Blend) mit Struktur 5a;

Fig.15:

Mikroskopiebild: Querschnitt Polyurethan-beschichteter Träger aus Makroblend® UT6405 SG (Polycarbonat/Polyester-Blend) mit Struktur 5c;

Fig.16:

Mikroskopiebild: Querschnitt Polyurethan-beschichteter Träger aus Makroblend® UT6405 SG (Polycarbonat/Polyester-Blend) mit Struktur 5b;

Fig. 17:

Mikroskopiebild: Querschnitt Polyurethan-beschichteter Träger aus Bayblend® T85 SG (Polycarbonat/ABS-Blend) mit Schleifpapierstruktur 6a;

Fig. 18:

Mikroskopiebild: Querschnitt Polyurethan-beschichteter Träger aus Bayblend® T85 SG (Polycarbonat/ABS-Blend) mit Schleifpapierstruktur 6b;

Fig. 19:

Mikroskopiebild: Querschnitt Polyurethan-beschichteter Träger aus Bayblend® T85 SG (Polycarbonat/ABS-Blend) mit Schleifpapierstruktur 6c;

Fig. 20:

Mikroskopiebild: Querschnitt Polyurethan-beschichteter Träger aus Makroblend@ UT6405 SG (Polycarbonat/ABS-Blend) mit Schleifpapierstruktur 6a;

Fig. 21:

Mikroskopiebild: Querschnitt Polyurethan-beschichteter Träger aus Makroblend® UT6405 SG (Polycarbonat/ABS-Blend) mit Schleifpapierstruktur 6b;

Fig. 22:

Mikroskopiebild: Querschnitt Polyurethan-beschichteter Träger aus Makroblend@ UT6405 SG (Polycarbonat/ABS-Blend) mit Schleifpapierstruktur 6c;

Fig. 23:

Mikroskopiebild: Querschnitt Polyurethan-beschichteter Träger aus Bayblend® T85 SG (Polycarbonat/ABS-Blend) mit Feilenstruktur 7a;

Fig. 24:

Mikroskopiebild: Querschnitt Polyurethan-beschichteter Träger aus Bayblend® T85 SG (Polycarbonat/ABS-Blend) mit Feilenstruktur 7b;

Fig. 25:

Mikroskopiebild: Querschnitt Polyurethan-beschichteter Träger aus Bayblend® T85 SG (Polycarbonat/ABS-Blend) mit Feilenstruktur 7c;

Fig. 26:

Mikroskopiebild: Querschnitt Polyurethan-beschichteter Träger aus Makroblend@ UT6405 SG (Polycarbonat/ABS-Blend) mit Feilenstruktur 7a;

Fig. 27:

Mikroskopiebild: Querschnitt Polyurethan-beschichteter Träger aus Makroblend® UT6405 SG (Polycarbonat/ABS-Blend) mit Feilenstruktur 7b;

Fig. 28:

Mikroskopiebild: Querschnitt Polyurethan-beschichteter Träger aus Makroblend® UT6405 SG (Polycarbonat/ABS-Blend) mit Feilenstruktur 7c.

Show it:

Fig. 1:

the inventive method for producing a composite part;

Fig. 2:

Structures on the tool surface;

3:

Microscopic picture: Cross-section of polyurethane-coated carrier made of Bayblend® T85 SG (polycarbonate / ABS blend) with erosion structure, VDI 33;

4:

Microscopic picture: Cross-section of polyurethane-coated carrier made of Bayblend® T85 SG (polycarbonate / ABS blend) with erosion structure, VDI 42;

Fig. 5:

Microscopy image: Cross-section of polyurethane-coated carrier made of Makroblend® UT6405 SG (polycarbonate / polyester blend) with point structure 3a;

Fig. 6:

Microscopic picture: Cross-section of polyurethane-coated carrier made of Makroblend® UT6405 SG (polycarbonate / polyester blend) with dot structure 3b;

Fig. 7:

Microscopy image: Cross-section of polyurethane-coated carrier made of Makroblend® UT6405 SG (polycarbonate / polyester blend) with dot structure 3c;

Fig. 8:

Microscopic picture: Cross-section of polyurethane-coated carrier made of Bayblend® T85 SG (polycarbonate / ABS blend) with rhombic structure 4a;

Fig. 9:

Microscopic picture: cross-section of polyurethane-coated carrier made of Bayblend® T85 SG (polycarbonate / ABS blend) with diamond structure 4b;

Fig. 10:

Microscopic picture: Cross-section of polyurethane coated carrier made of Bayblend® T85 SG (polycarbonate / ABS blend) with diamond structure 4c;

Fig. 11:

Microscopic picture: Cross section of polyurethane-coated carrier made of Bayblend® T85 SG (polycarbonate / ABS blend) with structure 5a;

Fig. 12:

Microscopy image: Cross section of polyurethane-coated carrier made of Bayblend® T85 SG (polycarbonate / ABS blend) with structure 5c;

Fig. 13:

Microscopy image: Cross section of polyurethane-coated carrier made of Bayblend® T85 SG (polycarbonate / ABS blend) with structure 5b;

Figure 14:

Microscopic picture: Cross section of polyurethane-coated carrier made of Makroblend® UT6405 SG (polycarbonate / polyester blend) with structure 5a;

Figure 15:

Microscopic picture: Cross-section of polyurethane-coated carrier made of Makroblend® UT6405 SG (polycarbonate / polyester blend) with structure 5c;

Figure 16:

Microscopic picture: Cross-section of polyurethane-coated carrier made of Makroblend® UT6405 SG (polycarbonate / polyester blend) with structure 5b;

Fig. 17:

Microscopic picture: Cross-section of polyurethane-coated carrier made of Bayblend® T85 SG (polycarbonate / ABS blend) with sandpaper structure 6a;

Fig. 18:

Microscopic picture: Cross-section of polyurethane-coated carrier made of Bayblend® T85 SG (polycarbonate / ABS blend) with sandpaper structure 6b;

Fig. 19:

Microscopic picture: Cross section of polyurethane-coated carrier made of Bayblend® T85 SG (polycarbonate / ABS blend) with sandpaper structure 6c;

Fig. 20:

Microscopic picture: Cross-section of polyurethane-coated support made of Makroblend @ UT6405 SG (polycarbonate / ABS blend) with sandpaper structure 6a;

Fig. 21:

Microscopic picture: Cross-section of polyurethane-coated carrier made of Makroblend® UT6405 SG (polycarbonate / ABS blend) with sandpaper structure 6b;

Fig. 22:

Microscopic picture: Cross-section of polyurethane-coated support made of Makroblend @ UT6405 SG (polycarbonate / ABS blend) with sandpaper structure 6c;

Fig. 23:

Microscopic picture: Cross-section of polyurethane-coated carrier made of Bayblend® T85 SG (polycarbonate / ABS blend) with file structure 7a;

Fig. 24:

Microscopic picture: Cross-section of polyurethane-coated carrier made of Bayblend® T85 SG (polycarbonate / ABS blend) with file structure 7b;

Fig. 25:

Microscopic picture: Cross-section Polyurethane-coated carrier made of Bayblend® T85 SG (polycarbonate / ABS blend) with file structure 7c;

Fig. 26:

Microscopic picture: Cross-section of polyurethane-coated carrier made of Makroblend @ UT6405 SG (polycarbonate / ABS blend) with file structure 7a;

Fig. 27:

Microscopic picture: Cross-section of polyurethane-coated carrier made of Makroblend® UT6405 SG (polycarbonate / ABS blend) with file structure 7b;

Fig. 28:

Microscopic picture: Cross-section of polyurethane-coated carrier made of Makroblend® UT6405 SG (polycarbonate / ABS blend) with file structure 7c.

FIG. 1 shows the inventive method for producing the composite components 1 according to the invention, wherein by way of example for the coating (second layer) 2 is spoken by a polyurethane coating. For this purpose, the thermoplastic resin granules are melted in an injection cylinder and injected at a temperature of 270 ° C in the first mold cavity 4 of the closed tool 5 (steps 1 and 2 in FIG. 1 ). This first mold cavity 4 is preferably tempered to 70 to 90 ° C. The walls of the tool 5, which this cavity 4 envelop, have at least partially structured surfaces 6, which image on the carrier (structure 7 on the carrier surface). After expiration of the holding pressure time and cooling time during which the carrier 3 solidifies, the tool 5 is opened in a further method step (step 3 in FIG FIG. 1 ). In this case, the carrier 3, which has at least partially a structured surface 7, held on the ejector side of the injection mold 5 and from the carrier position complete with the tool core via a slider 8 in the coating position (step 4 in FIG FIG. 1 ). The injection mold 5 is closed again (step 5 in FIG FIG. 1 ), a closing force is built up and in the next method step the reactive coating system is injected into the coating cavity 9 under a pressure of generally up to 200 bar (step 6 in FIG FIG. 1 ). The reactive components of the coating system are thereby promoted by the RIM system in a high-pressure countercurrent mixing head and mixed there before injection. The coating-side cavity is preferably tempered to a temperature of 70 to 100 ° C. After the end of the injection, it is preferable to seal the injection nozzle of the mixing head for the coating composition by means of a hydraulic cylinder to prevent backflow of the coating material. After expiry of the reaction and cooling time, the tool 5 is opened again in a further method step (step 7 in FIG FIG. 1 ) and the coated molding (composite part) 1 (step 8 in FIG. 1 ).

FIG. 2 shows various structurings which can be used to improve the adhesion between the support and the coating. Due to the better reproducibility, the thermoplastic support with structured surface was photographed in part, but instead the tool that forms the first cavity into which the thermoplastic is injected for curing.

Not shown is the conventional surface structure of a thermoplastic carrier made in a tool with a smooth inner surface. The surface structure of such a carrier is also smooth. A support having such a conventional surface was used for the comparative experiments.

The structures 2a and 2b show different surfaces of the tool surface. The structure 2a is formed by fine erosion (VDI 33) of the surface, the structure 2b by coarse erosion (VDI 42). The structures 3a, 3b and 3c are dot patterns with a texture depth of 85 μm, 150 μm and 250 μm, respectively. The structures 4a, 4b and 4c are diamond patterns with a texture depth of 70 μm, 150 μm and 250 μm, respectively. The structures of the tool surfaces described below were obtained by pressing a silicone impression of a corresponding structure (for example a microfiber cloth) into the not yet hardened obtained ceramic surface, which was then cured. The structures 5a, 5b and 5c are modeled on textile structures. The structures 5a and 5c are formed, for example, by embossing with different seat covers. The structure 5b has the structure of a microfiber cloth. The structures 6a, 6b and 6c are abrasive paper structures, those of fine 180 grit abrasive paper (structure 6a), 60 grit middle grit paper (structure 6b) and 40 grit coarse grit paper (structure 6c). The structures 7a, 7b and 7c are file structures. Structure 7a is a flat stump file structure cut 1 (fine cut). This is also obtained as described above for structure 5b. The structure 7b results accordingly by a flat butt joint cut 2 (middle cut). The structure 7c results from a milled file with a chop 2 (coarse file).

The FIGS. 3 to 28 show microscopic images of cross-sections through the layers of various composite parts, a support of Bayblend® T85 SG (polycarbonate / acrylonitrile-butadiene-styrene copolymer blend) or Makroblend®UT 6405 SG (polycarbonate / polyester blend), different structuring and a polyurethane coating exhibit. The production of the composite parts was carried out as described below under "Examples". The structures used to form the surfaces in contact with the polyurethane varnish correspond to those in US Pat FIG. 2 shown.

The microscope images were taken with the Axioplan device from Zeiss. At a 50-fold magnification, the 11 to FIG. 28 and a 100x magnification the Fig. 3 to 10 , All these figures ( 3 to FIG. 28 ) were generated by reflected light and dark field.

The FIGS. 3 and 4 show sectional views of the molded erosion structures according to VDI 33 and VDI 44. They are characterized by irregular, soft, wave-like elevations of the surface. There are no sharp edges and small radii. With a finger crossed over the structure feels FIG. 3 smooth and even on, the structure off FIG. 4 feels smooth but uneven.

The FIGS. 5 to 7 show the sectional images of a dot-grid structure. They are characterized by a regular structure. The structure out FIG. 5 with a mean structure depth of 85 μm is characterized by semicircular valleys and rounded plateaus with a width of approx. 300 μm. The radii at the foot of the dot structure are off at the structure FIG. 6 with on average 150 μm structure depth significantly smaller than in the structure FIG. 5 and at FIG. 7 with on average 250 μm structure depth smallest. All bitmap patterns show no sharp edges or undercut structures. Characteristic is a smooth lines.

The FIGS. 8 to 10 show the sectional images of the rhombic structure, which viewed in section from the side with the structures of the FIGS. 5 to 7 are comparable. In the plan view in Fig. 2 you recognize the rhombuses.

The sectional images of the molded textiles are in the FIGS. 11 to 16 shown. The structures are characterized by an irregular, rugged surface. The radii of the structures are small to sharp-edged, the lines of the surface are irregular and have cracks. In part, undercut structures are visible.

The FIGS. 20 to 22 show the sectional views of the sandpaper structures in different grain sizes. All structures are characterized by an irregular, rough surface with partially undercut structures. Especially with the coarsest structure in FIG. 22 are very steep flanks to recognize.

The FIGS. 23 to 28 show the structures of the file geometry. The surface is characterized by regular, relatively smooth structures. The angles of the teeth are characterized in that one side is formed very flat and the other side almost perpendicular to the surface drops, sometimes slightly undercut. The depth of the elevations of a single filing tooth is, in some cases over 500 μm, relatively high compared to the other structures.

Examples

The granules resulting from the respective compounding were fed to the Battenfeld HM270 / 1330 S Unilog B4 injection molding machine.

There were partially surface coated moldings with a projected area of about 200 (length: about 163 mm, width: about 125 mm) cm ² on the injection molding machine in an injection mold with two cavities (a substrate side cavity and a polyurethane side coating cavity, the linked to a RIM unit), as in FIG. 1 shown and described above. The composite part is a plate-shaped component made of thermoplastic material (carrier) whose surface has been partially coated with a polyurethane varnish. The wall thickness of the carrier molding was about 4 mm. The polyurethane layer thickness was about 0.3 mm.

• Bayblend® T85 SG (Polycarbonat/Acrylnitril-Butadien-Styrol-Copolymerisat-Blend) von Bayer MaterialScience AG, Leverkusen, Deutschland;
• Makroblend@ UT 6405 SG (Polycarbonat/Polyester-Blend) von Bayer MaterialScience AG, Leverkusen, Deutschland.

For the carrier, one of the following was used as the thermoplastic material:

• Bayblend® T85 SG (polycarbonate / acrylonitrile-butadiene-styrene copolymer blend) from Bayer MaterialScience AG, Leverkusen, Germany;
• Makroblend @ UT 6405 SG (polycarbonate / polyester blend) from Bayer MaterialScience AG, Leverkusen, Germany.

Makroblend®, ie polycarbonate / polyester blend, whose surface has not been structured, shows a much better adhesion compared to a polycarbonate blend with ABS. In order to be able to investigate the effect of structuring, it was necessary to pretreat the polycarbonate / polyester blend (Makroblend® UT 6405 SG) in such a way that an effect could be observed. For this purpose, the support from Makroblend®UT 6405 SG was first heated to 60 ° C. over a period of 48 hours and then aged for three cycles in the temperature cycling test, in a climate chamber type PL-4KPH from Espec. For carriers made of Bayblend® T85 SG, on the other hand, only in the case of structures 3c and 4c did pretreatment also take place over a period of 48 hours at 60 ° C., followed by aging for three cycles in the temperature cycling test.

Each aging cycle included the following temperature profile: 105 ° C for 15 h, then 23 ± 2 ° C for 30 min, then -40 ° C for 8 h, then 23 ± 2 ° C for 30 min.

• Desmophen® XP 2488 (ein verzweigtes Polyesterpolyol, enthaltend 1,4'-Bishydroxymethyl-cyclohexan) von Bayer MaterialScience AG, Leverkusen, Deutschland,
• Desmodur® N 3600 (ein aliphatisches Polyisocyanat, und zwar niedrigviskoses Hexamethylen-1,6-diisocyanat-Trimerisat, molare Masse: 504 g/mol) von Bayer MaterialScience AG, Leverkusen,
• 0,5% Dibutylzinndilaurat.

The material used for the coating was a reactive polyurethane raw material mixture which was a mixture of the following components:

• Desmophen® XP 2488 (a branched polyester polyol containing 1,4'-bishydroxymethyl cyclohexane) from Bayer MaterialScience AG, Leverkusen, Germany
• Desmodur® N 3600 (an aliphatic polyisocyanate, namely low-viscosity hexamethylene-1,6-diisocyanate trimer, molar mass: 504 g / mol) from Bayer MaterialScience AG, Leverkusen, Germany
• 0.5% dibutyltin dilaurate.

The composite adhesion between the backing and the polyurethane coating was tested on 25 mm sample strips which were sawn from the partially PU coated 2-component composite panels by a roller peel test according to DIN EN 1464 at a test speed of 100 mm / min determined. <b> Table 1: </ b> Influence of the surface structure of the support on the adhesion of the coating Adhesion [N / mm] without structuring, 0.41 Bayblend® T85 SG Structure 3a, dot matrix 85 μm 0.85 Bayblend® T85 SG Structure 3b, dot matrix 150 μm 1.78 Bayblend® T85 SG Structure 3c, dot matrix 250 μm excellent adhesion Bayblend® T85 SG Structure 4a, diamond grid 70 μm 0.45 Bayblend® T85 SG Structure 4b, diamond grid 150 μm 0.70 Bayblend® T85 SG Structure 4c, diamond grid 250 μm excellent adhesion Bayblend® T85 SG without structuring, 0.14 Makroblend® UT 6405 SG Structure 2a, erosion structure, VDI 33, 0.19 Makroblend® UT 6405 SG Structure 2b, erosion structure VDI 42, 0.20 Makroblend® UT 6405 SG Structure 3a, dot matrix 85 μm 0.25 Makroblend® UT 6405 SG Structure 3b, dot matrix 150 μm excellent adhesion Makroblend® UT 6405 SG Structure 3c, dot matrix 250 μm excellent adhesion Makroblend® UT 6405 SG Structure 4a, diamond grid 70 μm 0.23 Makroblend® UT 6405 SG Structure 4b, diamond grid 150 μm 0.42 Makroblend® UT 6405 SG Structure 4c, diamond grid 250 μm 0.48 Makroblend® UT 6405 SG

It can be seen from the table that any structuring surprisingly leads to a marked improvement in the adhesion between the support and the coating. When imprinted by Makroblend® UT 6405 SG after aging with a dot pattern with a grid depth of 150 or 250 μm (structures 3b and 3c) and Bayblend® T85 SG with a dot pattern or with a diamond pattern, each with a grid depth of 250 μm (structure 3c or Structure 4c) the adhesion improvement is even so outstanding that the polyurethane coating used in the roller peeling test can no longer be removed from the carrier made of thermoplastic material.

In the case of the structuring of the surfaces of the carriers with the structures 5a, 5b, 5c, 6a, 6b, 6c, 7a, 7b, 7c, an outstanding improvement of the adhesion between carrier and coating was achieved in this way, that it is the same for both the polycarbonate / ABS Blend (Bayblend® T85 SG) and in the case of the polycarbonate / polyester blend (Makroblend® UT 6405 SG), even with 6 aging cycles in the temperature cycling test, it was not possible to detach the polyurethane coating from the thermoplastic support in the roller peeling test.

Claims (9)

Method for producing a composite component comprising a support of a thermoplastic composition and a second layer on the support, wherein the surface of the carrier adjacent to the second layer is structured,
the method comprising the following steps following one another in this order: (i) injecting the melt of the thermoplastic composition into a first mold cavity for the production of the thermoplastic carrier, (ii) cooling the melt, (iii) enlarging the cavity of the injection molding tool to produce a gap space, (iv) injecting a mixture of raw materials to form the second layer in said gap space between the thermoplastic carrier and the tool surface, wherein the raw material mixture polymerizes to form the second layer in direct contact with the surface of the thermoplastic carrier, (v) demolding the composite part from the tool cavity, characterized in that the tool into which the thermoplastic composition is injected has, on its inner surface, a structure deviating from a smooth surface, by which the surface of the thermoplastic carrier obtains a structure. Method according to claim 1,
characterized in that the tool used to make the thermoplastic carrier comprises a ceramic surface. Method according to one of claims 1 or 2,
characterized in that the tool has received the structure on its surface by embossing, milling, eroding and / or lasers. Method according to one of the preceding claims,
characterized in that the tool as a structure, by which the surface of the thermoplastic carrier receives a structure, an erosion structure, a dot matrix, a diamond grid, a textile structure, a sandpaper structure and / or a file structure receives. Method according to one of the preceding claims,
characterized in that the structure in the surface of the carrier has been obtained by embossing with a tool. Method according to one of the preceding claims,
characterized in that the thermoplastic composition is a polycarbonate, a polystyrene, a styrene copolymer, an aromatic polyester, a polyolefin, a polyacrylate or copolyacrylate, a polymethacrylate or copolymer methacrylate, a styrene-acrylonitrile copolymer, a thermoplastic polymer, a polymer based on cyclic olefins, a polyamide or a mixture of said polymers. Method according to one of the preceding claims,
characterized in that the thermoplastic is a polycarbonate or a polycarbonate blend. Method according to one of the preceding claims,
characterized in that the raw material mixture for forming the second layer at least one polyisocyanate component, at least one H-active compound and - Optionally contains at least one polyurethane additive and / or processing aid. Method according to one of the preceding claims, characterized in that the second layer is a coating of a polyurethane hardcoat, polyurethane soft paint, a polyurethane skin or a polyurethane foam.

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